Phosphoric ester demulsifier composition

ABSTRACT

A phosphoric ester demulsifier composition prepared by reacting one or more alkylphenol-formaldehyde resin alkoxylates or one or more polyalkylene glycols, or a mixture thereof, with about 0.001 to about 1.0 molar equivalents of one or more phosphorous compounds selected from phosphorous oxychloride, phosphorous pentoxide and phosphoric acid and a method of using the demulsifier composition to resolve water-in-oil emulsions.

CROSS REFERENCE TO RELATED APPLICATIONS

This is a divisional of Ser. No. 10/389,447, filed Mar. 14, 2003.

TECHNICAL FIELD

This invention relates to compositions and methods of resolvingwater-in-oil emulsions. More particularly, this invention concernsphosphoric esters of alkylphenol-formaldehyde resin alkoxylates and/orpolylakylene glycols and use of the phosphoric esters to resolvewater-in-oil emulsions, particularly emulsions of water in crude oil.

BACKGROUND OF THE INVENTION

Crude oil produced from the geological formations can contain variousamounts of water. Water and crude oil are naturally non-miscible.However, when naturally occurring interfacial active compounds arepresent, these compounds can aggregate on the oil and water interfaceand cause water to form droplets within the bulk oil phase. During crudeoil lifting through production tubings, the oil and water encounters anincreased mixing energy from rapid flow through chokes and bends. Thisadditional mixing energy can emulsify the oil and water. This oilexternal, water internal two phase system is commonly referred to ascrude oil emulsion. This emulsion can be quite stable. However, thepresence of water in crude oil can interfere with refining operations,induce corrosion, increase heat capacity and reduce the handlingcapacity of pipelines and refining equipment. Therefore, The crude oilthat is to be shipped out of the oilfield should be practically free ofwater and usually has a maximum water content limit of about threepercent, depending on the type of crude and oil company.

The emulsified water can also contain various amounts of salts. Thesesalts are detrimental to crude oil refining processes due to potentialcorrosion in the refinery. In crude oil refining, desalting techniquescomprise the deliberate mixing of the incoming crude oil with a fresh“wash water” to extract the water soluble salts and hydrophilic solidstherefrom.

Primary dehydration of the crude oil occurs in oil field water oilseparation systems such as “free water knock out” and “phaseseparators”. Quite often these systems are not adequate for efficientseparation due to factors such as over production, unexpected productionchanges and system underdesigns. In these cases, emulsion breakingchemicals are added to the production processes to assist and promoterapid water oil separations.

Commonly used emulsion breaking chemicals include alkylphenolformaldehyde resin alkoxylate (AFRA), polyalkylene glycol (PAG), organicsulfonates, and the like. These compounds, however, may not providesatisfactory performance in all instances. Accordingly, there is anongoing need for new, economical and effective chemicals and processesfor resolving emulsions into their component parts of oil and water orbrine.

SUMMARY OF THE INVENTION

This invention is a phosphoric ester demulsifier composition prepared byreacting one or more alkylphenol-formaldehyde resin alkoxylates or oneor more polyalkylene glycols, or a mixture thereof, with about 0.001 toabout 1.0 molar equivalents of one or more phosphorous compoundsselected from phosphorous oxychloride, phosphorous pentoxide andphosphoric acid.

The phosphoric ester demulsifier of this invention can improve theperformance of currently used demulsifers by providing more rapid waterseparation as well as lower basic sediments and water (BS&W) in theshipping crude.

DETAILED DESCRIPTION OF THE INVENTION

The phosphoric ester demulsifier composition of this invention isprepared by reacting one or more alkylphenol-formaldehyde resinalkoxylates or one or more polyalkylene glycols, or a mixture thereof,with up to about one molar equivalent of a phosphorous compound selectedfrom phosphorous oxychloride, phosphorous pentoxide or phosphoric acid.If too much phosphorous compound is used, the resulting phosphoric estercomposition gels as a result of excessive cross linking. Accordingly,the amount of phosphorous compound used may be empirically determined asthe amount required to impart the desired demulsifying characteristicsto the composition while simultaneously avoiding gelling of thecomposition.

In a preferred aspect this invention, the alkylphenol-formaldehyde resinalkoxylate or polyalkylene glycol is reacted with about 0.01 to about0.5 molar equivalents of the phosphorous compound. A preferredphosphorous compound is phosphorous oxychloride.

The reaction is preferably conducted by heating a solution of thealkylphenol-formaldehyde resin alkoxylates or polyalkylene glycols in asuitable solvent to a temperature of about 60° C. to about 85° C.,preferably about 70° C. and then adding the phosphorous compound inportions. The reaction mixture is then heated for about one to aboutthree hours. When the phosphorous compound is phosphorous oxychloride,the reactor is purged with nitrogen during the course of the reaction todrive off HCl gas as it is formed.

Suitable solvents include aliphatic solvents such as kerosene and dieseland aromatic solvents such as xylene, toluene and light or heavyaromatic naphtha. Aromatic solvents are preferred.

The resulting phosphoric ester comprises a mixture of mono-, di-, ortri-phosphate esters where the proportion of these components depends onthe reaction conditions. In addition, cross-linked species can existdepending on the amount of reacting components.

Accordingly, in an aspect, this invention is a method of preparing aphosphoric ester demulsifier composition comprising reacting one or morealkylphenol-formaldehyde resin alkoxylates or one or more polyalkyleneglycols, or a mixture thereof, with about 0.001 to about 1 molarequivalents of one or more phosphorous compounds selected fromphosphorous oxychloride, phosphorous pentoxide and phosphoric acid.

“Alkylphenol-formaldehyde resin alkoxylate” means the reaction productof one or more alkylphenol-formaldehyde resins as described herein withabout 10 to about 500 molar equivalents of ethylene oxide and/orpropylene oxide under heat and pressure in the presence of an acid, baseor metallic catalyst. A preferred catalyst is potassium hydroxide.Preferably the reaction is conducted at a temperature of about 120° C.to about 180° C. and a pressure of about 80 psi. The reaction may beconducted neat or in a suitable solvent such as xylene, toluene, lightor heavy aromatic naphtha, and the like.

In cases where the alkylphenol-formaldehyde resin is reacted with bothethylene oxide and propylene oxide, the ethylene oxide and propyleneoxide may be added in random or block fashion.

Random addition of ethylene oxide and propylene oxide involves bothcomponents being added to the resin simultaneously, such that the rateof addition to the resin is controlled by their relative amounts andreaction rates. An alkoxylate prepared by random addition of ethyleneoxide and propylene oxide or by addition of a mixture of propylene oxideand ethylene oxide is referred to herein as a “mixed copolymer”.

In the case of block addition, either the ethylene oxide or propyleneoxide is added first to the resin and allowed to react. The othercomponent is then added and allowed to react. An alkoxylate prepared byblock addition of ethylene oxide and propylene oxide is referred toherein as a “block copolymer”.

Preferred alkylphenol-formaldehyde resin alkoxylates are selected fromthe group consisting of nonylphenol-formaldehyde resin alkoxylate,butylphenol-formaldehyde resin alkoxylate and amylphenol-formaldehyderesin alkoxylate, or a mixture thereof. Nonylphenol-formaldehyde resinalkoxylate is more preferred.

Alkylphenol-formaldehyde resins are typically prepared by the acid orbase catalyzed condensation of an alkylphenol with formaldehyde. Alkylgroups are straight or branched and contain about 3 to about 18,preferably about 4 to about 12 carbon atoms.

Representative acid catalysts include dodecylbenzenesulfonic acid(DDBSA), toluene sulfonic acid, boron trifluoride, oxalic acid, and thelike. Representative base catalysts include potassium hydroxide, sodiummethoxide, sodium hydroxide, and the like. The alkylphenol-formaldehyderesins of this invention preferably have a molecular weight of about1,000 to about 50,000, preferably about 1,000 to about 10,000.

Alkylphenol-formaldehyde resins are well known intermediates used inmaking alkylphenol-formaldehyde alkoxylate emulsion breakers. They areroutinely manufactured by a number of companies including Ondeo NalcoEnergy Services, Sugar Land, Tex. and Uniqema, a division of ICI,Cleveland, England.

“Polyalkylene glycol” means the reaction product of one or more C₄-C₁₂glycols with ethylene oxide and/or propylene oxide. The ethylene oxideand propylene oxide can be added in random or block fashion as describedabove. The C₄-C₁₂ glycol may be straight or branched or cyclic andcontains from 2 to about 6 hydroxy groups. Representative glycolsinclude diethylene glycol, dipropylene glycol, sorbitol, sucrose,glucose, pentaerythritol, and the like. Diethylene glycol anddipropylene glycol are preferred.

Preferred polyalkylene glycols include C₄₋₁₂ glycol base polyethyleneglycols, C₄₋₁₂ glycol base polypropylene glycols, C₄₋₁₂ glycol basepolyethylene/polypropylene block copolymers, C₄₋₁₂ glycol basepolyethylene/polypropylene mixed copolymers and C₄₋₁₂ glycol basecross-linked polyalkylene glycols.

The polyalkylene glycols preferably have a molecular weight of about 100to about 100,000. Polyalkylene glycols are commercially available from avariety of suppliers including Ondeo Nalco Energy Services, Sugar Land,Tex.

The polyalkylene glycols and alkylphenol-formaldehyde resin alkoxylatesmay also be cross-linked by reaction with an agent having at least twofunctionalities capable of reacting with hydroxyl groups. Preferredcross linking agents include epoxides such as bisphenol Aepichlorohydrin, also known as4′4-isopropylidenediphenol-Epichlorohydrin Resin available from AshlandChemical Company, Columbus, Ohio and isocyanates such as toluene2,4-diisocyanate, available from Arco Chemical Company, Newtown Square,Pa.

The phosphoric ester composition of this invention is effective forresolving a broad range of hydrocarbon emulsions encountered in crudeoil production, refining and chemical processing. Typical hydrocarbonsinclude crude oil, refined oil, bitumen, condensate, slop oil,distillates, fuels and mixtures thereof. The polyester composition isalso useful for resolving emulsions in butadiene, styrene, acrylic acid,and other hydrocarbon monomer process streams.

In a preferred aspect of this invention, the phosphoric estercomposition is used to demulsify water-in-oil emulsions in variousproduction and refinery processes. In a refinery desalting process, theincoming crude is deliberately mixed with wash water to remove dissolvedsalts and other contaminants. To extract water from the resultingwater-in-crude oil emulsion, the emulsion is admixed with an effectiveamount of the phosphoric ester demulsifier of this invention.

In the process of resolving crude petroleum oil emulsions of thewater-in-oil type, the phosphoric ester demulsifying agent of theinvention is brought into contact with or caused to act upon theemulsion to be treated in any of the various methods now generally usedin the petroleum industry to resolve or break crude petroleum oilemulsions with a chemical agent.

The phosphoric ester demulsifier composition may be used alone, incombination with additional phosphoric ester demulsifiers or incombination with any of a number of additional demulsifiers known in theart including alcohols, fatty acids, fatty amines, glycols andalkylphenol formaldehyde condensation products. The phosphoric estercomposition may also be used in combination with corrosion inhibitors,viscosity reducers and other chemical treatments used in crude oilproduction, refining and chemical processing.

In a typical application, the phoshporic ester demulsifier(s) and anyadditional emulsion breaking chemicals are typically blended together ina suitable solvent for application to the emulsion. Representativesolvents include xylene, toluene, light or heavy aromatic naphtha, andthe like. Each component contributes to different treatingcharacteristics when added to the crude oil emulsion due to their uniquechemical properties.

The amount of phosphoric ester demulsifier used depends on theparticular crude oil emulsion being treated. Bottle tests as describedherein may be conducted on site in order to determine the optimum doseand formulation. In general, the effective amount of phosphoric esterdemulsifier ranges from about 50 ppm to 500 ppm based on the volume ofcrude production.

The phosphoric ester demulsifier is introduced into the crude oilemulsion by injecting beneath the surface into the oil well itself, byinjecting into the crude oil at the well-head or by injecting into thecrude oil process stream at a point between the well-head and the finaloil storage tank. The demulsifier composition may be injectedcontinuously or in batch fashion. The injecting is preferablyaccomplished using electric or gas pumps.

The treated crude oil emulsion is then allowed to stand in a quiescentstate until the desired separation into distinct layers of water and oilresults. Once separation into distinct layers of water and oil has beeneffected, various means known in the art can be utilized for withdrawingthe free water and separating crude oil.

In a typical process for demulsification of crude oil, a reservoir isprovided to hold the composition of the invention in either diluted orundiluted form adjacent to the point where the effluent crude petroleumoil leaves the well. For convenience, the reservoir is connected to aproportioning pump capable of dropwise injecting the demulsifier of theinvention into the fluids leaving the well, which then pass through aflow line into a settling tank. Generally, the well fluids pass into thesettling tank at the bottom of the tank so that incoming fluids do notdisturb stratification of the layers of crude petroleum oil and waterwhich takes place during the course of demulsification.

The foregoing may be better understood by reference to the followingexamples, which are presented for purposes of illustration and are notintended to limit the scope of this invention.

EXAMPLE 1

Preparation of a Nonylphenol-Formaldehyde Resin.

Nonylphenol (63.31% by weight) and heavy aromatic naphtha (27.69% byweight) are charged to a reactor and heated to 140-155° F. Oxalic acid(0.36% by weight) and ⅓ of the total amount of formaldehyde (2.88% byweight) are then added. The exothermic reaction is maintained at atemperature below 210° F. by cooling. After the exotherm subsides andthe reaction temperature reaches about 160° F. a second portion offormaldehyde (2.88% by weight) is added and the reaction temperature ismaintained between 160° F. and 210° F. A third portion of formaldehyde(2.88% by weight) is added when the reaction temperature again reachesabout 160° F. After all the formaldehyde is added, the reaction mixtureis heated at 210° F. for 3 hours and then the termperature is increasedto about 440° F. to distill off the water formed in the condensationreaction. The reaction is stopped when the desired molecular weight of2100-2700 (by GPC) is obtained.

EXAMPLE 2

Preparation of Nonylphenol-Formaldehyde Resin Alkoxylate (49.6%Propylene Oxide, 12.3% Ethylene Oxide).

Nonylphenol-formaldehyde resin (49.59% by weight, prepared as inExample 1) is charged into a reactor followed by 0.91% of heavy aromaticnaphtha (0.91% by weight). A 40 psig of nitrogen pad is maintainedthroughout the reaction period. KOH catalyst solution (0.40% by weight)is then added to the reactor. The reactor is then heated to 150° C. andpurged with nitrogen until the moisture content is less than about0.05%. Premixed ethylene oxide (36.82% by weight) and propylene oxide(12.28% by weight) are then added intermittently in small amounts, whilemaintaining a temperature of 150-160° C. and pressure not exceeding 70psig. The reaction is exothermic and cooling is required to keeptemperature and pressure in control. The reaction is stopped when allthe mixed oxide has been added.

EXAMPLE 3

Preparation of a Phosphate Ester of Nonylphenol-Formaldehyde ResinAlkoxylate (49.6% Propylene Oxide, 12.3% Ethylene Oxide).

Nonylphenol-formaldehyde resin alkoxylate (99.30% by weight, prepared asin Example 2) is added to a reactor. The reactor is then warmed to 70°C. and maintained at that temperature while phosphorous oxychloride(0.70% by weight) is added to the reactor. The components are thenallowed to mix and react for 30 minutes. A slight nitrogen purge is theninitiated into the fluid. The reaction continues for another 1.5 hoursand stops.

EXAMPLE 4

Preparation of Diproplyene Glycol Base Polyalkylene Glycol (82% byWeight Propylene Oxide, 16% by Weight Ethylene Oxide).

Dipropylene glycol (1.45% by weight) is charged into a reactor followedby KOH catalyst (0.52% by weight of a 45% aqueous KOH solution). Themixture is dehydrated by heating to 300° F. with repeated vacuum at −7psig and pressure up at 2 psig for two hours. The reactor is then set to260 deg ° F. and propylene oxide (82.03% by weight) is added at acontrolled rate to maintain a temperature of 260-285 deg ° F. and 40-110psig. When all of the propylene oxide has been added, the reactionmixture is heated to 300° F. and ethylene oxide (16.00% by weight) isadded at a controlled rate to maintain temperature between 310° F. and350° F. and 40-72 psig. After all of the ethylene oxide has been added,heating is continued at 310-F for 30 minutes.

EXAMPLE 5

Preparation of a Phosphate Ester of Diproplyene Glycol Base PolyalkyleneGlycol (82% by Weight Propylene Oxide, 16% by Weight Ethylene Oxide).

Diproplyene glycol base polyalkylene glycol (99.20% by weight, preparedas in Example 4) is added to a reactor. The reactor is then warmed to70° C. and maintained at that temperature while phosphorous oxychloride(0.80% by weight) is added to the reactor. The components are thenallowed to mix and react for 30 minutes. A slight nitrogen purge is theninitiated into the fluid. The reaction continues for another 1.5 hoursand stops.

Representative phosphoric ester demulsifier compositions preparedaccording to the methods described herein are shown in Table 1. TABLE 1Representative Demulsifier Compositions Demulsifier Intermediate Wt. %POCl₃ 1 Sorbitol base polyalkylene glycol (11.6% 0.41 propylene oxide,58.2% ethylene oxide) 2 Sorbitol base polyalkylene glycol (11.6% 0propylene oxide, 58.2% ethylene oxide) 3 Diepoxide crosslinkeddipropylene glycol 2.06 base polyalkylene glycol (PPG 4000) with 54%propylene oxide 4 Diepoxide crosslinked dipropylene glycol 4.10 basepolyalkylene glycol (PPG 4000) with 54% propylene oxide 5 Diepoxidecrosslinked dipropylene glycol 6.15 base polyalkylene glycol (PPG 4000)with 54% propylene oxide 6 Diepoxide crosslinked dipropylene glycol 8.20base polyalkylene glycol (PPG 4000) with 54% propylene oxide 7 Diepoxidecrosslinked dipropylene glycol 0 base polyalkylene glycol (PPG 4000)with 54% propylene oxide 8 Diepoxide crosslinked dipropylene glycol 2.06base polyalkylene glycol (PPG 4000) with 6.3% ethylene oxide and 27%propylene oxide 9 Diepoxide crosslinked dipropylene glycol 4.11 basepolyalkylene glycol (PPG 4000) with 6.3% ethylene oxide and 27%propylene oxide 10 Diepoxide crosslinked dipropylene glycol 6.17 basepolyalkylene glycol (PPG 4000) with 6.3% ethylene oxide and 27%propylene oxide 11 Diepoxide crosslinked dipropylene glycol 8.23 basepolyalkylene glycol (PPG 4000) with 6.3% ethylene oxide and 27%propylene oxide 12 Diepoxide crosslinked dipropylene glycol 0 basepolyalkylene glycol (PPG 4000) with 6.3% ethylene oxide and 27%propylene oxide 13 A mixture of dipropylene glycol base 0.82polyalkylene glycol (82% propylene oxide, 16% ethylene oxide) andnonyl/dinonylphenol-formaldehyde resin alkoxylate (33% propylene oxide,25% ethylene oxide) 14 A mixture of dipropylene glycol base 1.23polyalkylene glycol (82% propylene oxide, 16% ethylene oxide) andnonyl/dinonylphenol-formaldehyde resin alkoxylate (33% propylene oxide,25% ethylene oxide) 15 A mixture of dipropylene glycol base 1.65polyalkylene glycol (82% propylene oxide, 16% ethylene oxide) andnonyl/dinonylphenol-formaldehyde resin alkoxylate (33% propylene oxide,25% ethylene oxide) 16 A mixture of dipropylene glycol base 0polyalkylene glycol (82% propylene oxide, 16% ethylene oxide) andnonyl/dinonylphenol-formaldehyde resin alkoxylate (33% propylene oxide,25% ethylene oxide) 17 A mixture of butylphenol-formaldehyde 0.73 resinalkoxylate (84% propylene oxide), dipropylene glycol base polyalkyleneglycol (95.5% propylene oxide, 1.2% ethylene oxide),butyl/nonylphenol-formaldehyde resin alkoxylate (10% propylene oxide,20% ethylene oxide) 18 A mixture of butylphenol-formaldehyde 1.10 resinalkoxylate (84% propylene oxide), dipropylene glycol base polyalkyleneglycol (95.5% propylene oxide, 1.2% ethylene oxide),butyl/nonylphenol-formaldehyde resin alkoxylate (10% propylene oxide,20% ethylene oxide) 19 A mixture of butylphenol-formaldehyde 1.46 resinalkoxylate (84% propylene oxide), dipropylene glycol base polyalkyleneglycol (95.5% propylene oxide, 1.2% ethylene oxide),butyl/nonylphenol-formaldehyde resin alkoxylate (10% propylene oxide,20% ethylene oxide) 20 A mixture of butylphenol-formaldehyde 2.19 resinalkoxylate (84% propylene oxide), dipropylene glycol base polyalkyleneglycol (95.5% propylene oxide, 1.2% ethylene oxide),butyl/nonylphenol-formaldehyde resin alkoxylate (10% propylene oxide,20% ethylene oxide) 21 A mixture of butylphenol-formaldehyde 2.20 resinalkoxylate (84% propylene oxide), dipropylene glycol base polyalkyleneglycol (95.5% propylene oxide, 1.2% ethylene oxide),butyl/nonylphenol-formaldehyde resin alkoxylate (10% propylene oxide,20% ethylene oxide) 22 A mixture of butylphenol-formaldehyde 4.39 resinalkoxylate (84% propylene oxide), dipropylene glycol base polyalkyleneglycol (95.5% propylene oxide, 1.2% ethylene oxide),butyl/nonylphenol-formaldehyde resin alkoxylate (10% propylene oxide,20% ethylene oxide) 23 A mixture of butylphenol-formaldehyde 0 resinalkoxylate (84% propylene oxide), dipropylene glycol base polyalkyleneglycol (95.5% propylene oxide, 1.2% ethylene oxide),butyl/nonylphenol-formaldehyde resin alkoxylate (10% propylene oxide,20% ethylene oxide) 24 A mixture of butylphenol-formaldehyde 1.10 resinalkoxylate (84% propylene oxide), dipropylene glycol base polyalkyleneglycol (95.5% propylene oxide, 1.2% ethylene oxide),nonylphenol-formaldehyde resin alkoxylate (12% propylene oxide, 36%ethylene oxide) 25 A mixture of butylphenol-formaldehyde 2.20 resinalkoxylate (84% propylene oxide), dipropylene glycol base polyalkyleneglycol (95.5% propylene oxide, 1.2% ethylene oxide),nonylphenol-formaldehyde resin alkoxylate (12% propylene oxide, 36%ethylene oxide) 26 A mixture of butylphenol-formaldehyde 0 resinalkoxylate (84% propylene oxide), dipropylene glycol base polyalkyleneglycol (95.5% propylene oxide, 1.2% ethylene oxide),nonylphenol-formaldehyde resin alkoxylate (12% propylene oxide, 36%ethylene oxide) 27 Nonylphenol-formaldehyde resin 1.87 alkoxylate (49.6%propylene oxide, 12.3% ethylene oxide) 28 Nonylphenol-formaldehyde resin2.81 alkoxylate (49.6% propylene oxide, 12.3% ethylene oxide) 29Nonylphenol-formaldehyde resin 3.75 alkoxylate (49.6% propylene oxide,12.3% ethylene oxide) 30 Nonylphenol-formaldehyde resin 0 alkoxylate(49.6% propylene oxide, 12.3% ethylene oxide)

EXAMPLE 6

Testing of Representative Phosphoric Ester Demulsifiers.

Crude emulsions from a United States west coast producing well arecollected and poured into 6-oz prescription bottles to the 100 ml mark.The crude emulsions have an API gravity of 15°. Representativephosphoric ester emulsion breaker treating compositions and unesterifiedcontrol compositions are added to the bottles and the bottles areagitated to mix the contents. Agitation is then stopped, the contentsare allowed to settle and the rate of water separation from oil isobserved and recorded. At the end of the testing period, depending onthe test requirement, either top oil, interface oil or a composite oilsample is thieved from the bottle and a centrifugation test is performedon the thieved sample to check for basic sediments and water. (BS&W—ameasure of unresolved emulsion).

The testing parameters, such as temperature, agitation, settling time,vary depending on the actual system. These parameters should be kept asclose to the actual production treating system as possible. The resultsare summarized in Table 2.

In Table 2, italicized data in indicates the instances where phosphoricester demulsifiers show equal or superior performance compared tostandard treatments. More water drop indicates a faster rate of wateroil separation. Lower BS&W indicates dryer oil. TABLE 2 PerformanceTesting of Representative Phoshoric Ester Demulsifier Compositions Waterdrop BS&W Demulsifier 1 hr 2 hr 15 hr BS W Slug 1 10 33 47 1.1 5.2 6.0 29 19 41 1.2 4.6 5.4 3 5 5 10 1.6 7.4 — 4 7 7 8 1.8 6.0 — 5 10 10 10 1.65.6 — 6 10 10 11 2.0 3.0 — 7 3 3 10 24.0 24.0 — 8 9 10 22 5.4 0.2 4.8 98 11 18 4.4 0.4 4.1 10 10 11 19 4.8 0.4 4.4 11 9 10 13 5.2 0.4 5.2 12 47 10 3.4 1.2 3.6 13 3 3 22 0.4 2.8 3.0 14 2 2 19 0.4 2.0 2.4 15 4 4 200.6 2.2 2.4 16 6 9 20 1.4 2.2 3.6 17 4 9 28 6.0 28.0 — 18 3 9 33 20.00.6 — 19 7 10 42 13.0 6.0 — 20 1 10 40 11.0 6.0 — 21 6 10 34 2.1 0.4 —22 5 9 32 2.2 2.0 — 23 1 4 19 4.0 4.0 — 24 8 26 45 0.2 5.8 6.0 25 6 1248 0.2 2.0 2.0 26 7 8 14 3.2 1.6 4.4 27 30 40 50 0.2 3.9 4.0 28 4 28 400.2 2.4 2.6 29 3 18 48 1.0 12.0 — 30 7 6 42 0.3 4.8 3.1

As shown in Table 2, the phosphoric ester demulsifier compositions ofthis invention exhibit comparable or superior performance when comparedto the corresponding demulsifiers which do not contain phosphoric esterlinkages.

Changes can be made in the composition, operation and arrangement of themethod of the present invention described herein without departing fromthe concept and scope of the invention as defined in the followingclaims:

1. A method of resolving a water-in-oil emulsion comprising adding tothe emulsion an effective demulsifying amount of a phosphoric esterdemulsifier composition prepared by reacting one or morealkylphenol-formaldehyde resin alkoxylates or one or more polyalkyleneglycols, or a mixture thereof, with about 0.001 to about 1.0 molarequivalents of one or more phosphorous compounds selected fromphosphorous oxychloride, phosphorous pentoxide and phosphoric acid. 2.The method of claim 1 wherein the alkylphenol-formaldehyde resinalkoxylate is selected from the group consisting ofnonylphenol-formaldehyde resin alkoxylate, butylphenol-formaldehyderesin alkoxylate and amylphenol-formaldehyde resin alkoxylate, or amixture thereof.
 3. The method of claim 1 wherein the polyalkyleneglycol is selected from the group consisting of C₄₋₁₂ glycol basepolyethylene glycols, C₄₋₁₂ glycol base polypropylene glycols, C₄₋₁₂glycol base polyethylene/polypropylene block copolymers, C₄₋₁₂ glycolbase polyethylene/polypropylene mixed copolymers and C₄₋₁₂ glycol basecross-linked polyalkylene glycols.
 4. The method of claim 1 wherein thepolyalkylene glycol and alkylphenol-formaldehyde resin alkoxylate arecross-linked by reaction with a cross linking agent having at least twofunctionalities capable of reacting with hydroxyl groups.
 5. The methodof claim 4 wherein the cross linking agent is bisphenol Aepichlorohydrin.
 6. The method of claim 1 wherein the phosphoriccompound is phosphorous oxychloride.
 7. The method of claim 1 whereinthe phosphoric ester is prepared by reacting one or morealkylphenol-formaldehyde resin alkoxylates with about 0.01 to about 0.5molar equivalents of phosphorous oxychloride.
 8. The method of claim 5wherein the alkylphenol-formaldehyde resin alkoxylate isnonylphenol-formaldehyde resin alkoxylate.
 9. The method of claim 1wherein the phosphoric ester is prepared by reacting one or morepolyalkylene glycols with about 0.01 to about 0.5 molar equivalents ofphosphorous oxychloride.
 10. The method of claim 1 wherein thephosphoric ester demulsifier composition comprises phosphoric ester anda hydrocarbon solvent.
 11. The method of claim 1 wherein thewater-in-oil emulsion is selected from the group consisting ofwater-in-oil emulsions encountered in crude oil production, crude oilrefining and chemical processing.
 12. The method of claim 11 wherein thewater-in-oil emulsion is a crude oil emulsion.
 13. The method of claim12 wherein the phosphoric ester composition is added to the crude oilemulsion by injecting beneath the surface into the oil well, byinjecting into the crude oil at the well-head or by injecting into thecrude oil process stream at a point between the well-head and the finaloil storage tank.
 14. The method of claim 12 wherein the phosphoricester composition is added to the crude oil emulsion in a refinerydesalting process.
 15. The method of claim 11 wherein the water-in-oilemulsion encountered in chemical processing is selected from the groupconsisiting of water-in-oil emulsions encountered in butadiene, styreneand acrylic acid process streams.
 16. The method of claim 1 furthercomprising adding one or more additional demulsifiers to the theemulsion.
 17. The method of claim 16 wherein the additional demulsifiersare blended with the phosphoric ester demulsifier composition.
 18. Themethod of claim 16 wherein the additional demulsifiers are selected fromthe group consisting of alcohols, fatty acids, fatty amines, glycols andalkylphenol formaldehyde condensation products.
 19. The method of claim1 further comprising adding one or more corrosion inhibitors to theemulsion.
 20. The method of claim 1 further comprising adding one ormore viscosity reducers to the emulsion.